Polythiophene (PTh)-based coordination complexes, polythiophene iron (PTh Fe) and polythiophene iron oxygen (PTh-Fe-O) were synthesized by chemical method and proved to be novel high-performance organometallic lithium-storage materials. Extended X-ray absorption fine structural (EXAFS) spectroscopy and density functional theory (DFT) calculations indicate that these complexes have layered structures. It is believed that the strong and stable Fe S coordination creates sites of lithium storage and ensures the high specific capacity and outstanding cycle performance of the PTh-based complexes. (C) 2013 Elsevier B.V. All rights reserved.